CN107001752B - Resin combination, film and display device - Google Patents

Abstract

The present invention provide it is a kind of be capable of forming with high dielectric constant, and even if in the environment of high temperature and humidity for a long time using be able to maintain the transparency film resin combination.Resin combination of the invention contains (methyl) acrylic resin and vinylidene fluoride resin, wherein, 100 mass % of summation relative to (methyl) acrylic resin and vinylidene fluoride resin, contain 35~45 mass % (methyl) acrylic resins and 65~55 mass % vinylidene fluoride resins respectively, the weight average molecular weight (Mw) for being somebody's turn to do (methyl) acrylic resin is 100, 000~300, 000, at least one resin contained by resin combination contains alkali metal, 100 mass parts of total amount relative to all resins contained by resin combination and alkali metal, the content of alkali metal is 50ppm or less.

Description

Resin combination, film and display device

Technical field

The present invention relates to resin combination, film and display devices.

Background technique

In recent years, in the display devices such as smart phone, portable game machine, audio player, tablet computer terminal, have The display device of touch screen is being continuously increased.On the surface of this kind of display device, usually using glass sheet, but from display It sets out in terms of the light-weighted tendency of device, processability, is carrying out the plastic sheet of the substitute as glass sheet Exploitation.For example, in patent document 1, the plastic sheet of the substitute as glass sheet is disclosed containing methacrylic tree The clear sheet of rouge and vinylidene fluoride resin describes the clear sheet and fully meets the transparency and dielectric constant.

On the other hand, in recent years, display device is used under various environment due to its high versatility, thus It needs that there is durability under the harsh environment such as such as high temperature and humidity.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-244604 bulletin

Summary of the invention

Problem to be solved by the invention

This kind of previous clear sheet described in Patent Document 1, the high temperature as such as 60 DEG C and relative humidity 90% There is gonorrhoea phenomenon in the environment of high humidity, there are also rooms for improvement for durability.

The method for solving problem

The present invention be in view of the above problems obtained from.That is, the present invention includes the hair recorded in [1] below~[20] It is bright.

[1] a kind of resin combination contains (methyl) acrylic resin and vinylidene fluoride resin, wherein

Relative to the 100 mass % of summation of (methyl) acrylic resin and vinylidene fluoride resin, respectively containing 35~ 45 mass % (methyl) acrylic resins and 65~55 mass % vinylidene fluoride resins are somebody's turn to do (methyl) acrylic resin Weight average molecular weight (Mw) is 100,000~300,000,

At least one resin contained by resin combination contains alkali metal, relative to all resins contained by resin combination With 100 mass parts of total amount of alkali metal, the content of alkali metal is 50ppm or less.

[2] resin combination recorded in [1], wherein (methyl) acrylic resin is (a1) or (a2) below Resin,

(a1) homopolymer of methyl methacrylate,

(a2) come containing 50~99.9 mass % from the structural unit of methyl methacrylate and 0.1~50 mass % Derived from the copolymer of at least one structural unit of (methyl) acrylate indicated by following formula (1),

In formula, R₁Indicate hydrogen atom or methyl, R₁R when for hydrogen atom₂Indicate the alkyl of carbon number 1~8, R₁R when for methyl₂Table Show the alkyl of carbon number 2~8.

[3] resin combination recorded in [1] or [2], wherein the weight average molecular weight (Mw) of (methyl) acrylic resin It is 120,000~250,000.

[4] resin combination that any one of [1]~[3] are recorded, wherein vinylidene fluoride resin is to gather inclined difluoro second Alkene.

[5] resin combination that any one of [1]~[4] are recorded, wherein the melt mass flow of vinylidene fluoride resin Rate is 0.1~30g/10 minutes.

[6] resin combination that any one of [1]~[5] are recorded, wherein the resin combination also contains colorant.

[7] a kind of film contains the layer formed by the resin combination that any one of [1]~[6] are recorded.

[8] film recorded in [7], wherein the film with a thickness of 100~2000 μm.

[9] film recorded in [7] or [8], wherein the film also contains thermoplastic resin layer.

[10] film that any one of [7]~[9] are recorded, wherein contain heat on the two sides of the layer formed by resin combination Plastic resin layers.

[11] film recorded in [9] or [10], wherein thermoplastic resin layer is (methyl) acrylic resin or poly- carbon Acid ester resin layer.

[12] film that any one of [9]~[11] are recorded, wherein thermoplastic resin layer is by relative to forming the thermoplasticity The layer that the resin that 100 mass parts of all resins of resin layer contain 50 mass parts or more (methyl) acrylic resin is formed.

[13] film recorded in [11] or [12], wherein (methyl) acrylic resin contained by thermoplastic resin layer Weight average molecular weight is 50,000~300,000.

[14] any one of [9]~[13] record film, wherein thermoplastic resin layer with a thickness of 10~200 μm.

[15] film that any one of [9]~[14] are recorded, wherein the vicat softening temperature (Vicat of thermoplastic resin layer Softening Temperature) it is 100~160 DEG C.

[16] a kind of film contains (methyl) acrylic resin and vinylidene fluoride resin, wherein is exposed to the film When 120 hours in the environment of 60 DEG C and relative humidity 90%, the mist degree of the film be 2% hereinafter, and dielectric constant be 4.0 with On.

[17] film that any one of [7]~[16] are recorded, wherein at least one surface, there are also be selected from for assigning The coating of at least one of anti-scratch, antireflection, anti-dazzle and anti-fingerprint function.

[18] a kind of display device contains the film of any one of [7]~[17] record.

[19] a kind of polarization plates with film obtain for the film and polarization plates that any one of [7]~[17] are recorded is laminated.

[20] a kind of display device contains the polarization plates with film recorded in [19].

Invention effect

The layer formed by resin combination of the invention and the film containing this layer have a high dielectric constant, and even if For a long time using being also able to maintain the transparency in the environment of high temperature and humidity, therefore it can be used as the front panel of display device.

Detailed description of the invention

Fig. 1 is the skeleton diagram of the manufacturing device of the film of the invention used in embodiment.

Fig. 2 is the section for showing the layer configuration example of a preferred embodiment of liquid crystal display device according to the present invention Schematic diagram.

Specific embodiment

< resin combination >

Resin combination of the invention is the resin at least containing (methyl) acrylic resin and vinylidene fluoride resin Composition contains 35~45 relative to the 100 mass % of summation of (methyl) acrylic resin and vinylidene fluoride resin respectively Quality % (methyl) acrylic resin and 65~55 mass % vinylidene fluoride resins are somebody's turn to do the weight of (methyl) acrylic resin Average molecular weight (Mw) is 100,000~300,000.Also, at least one resin contained by the resin combination contains alkali metal, Relative to 100 mass parts of summation of all resins contained by resin combination and alkali metal, the content of alkali metal be 50ppm with Under.Hereinafter, the present invention will be described.

Summation 100 mass % of the resin combination relative to (methyl) acrylic resin and vinylidene fluoride resin, 37~45 mass % (methyl) acrylic resins and 55~63 mass % vinylidene fluoride resins are preferably comprised, further preferably 38~45 mass % (methyl) acrylic resins and 55~62 mass % vinylidene fluoride resins, further preferably 38~ 43 mass % (methyl) acrylic resins and 57~62 mass % vinylidene fluoride resins.As long as it should be noted that not It damages in the degree of the transparency, in addition to (methyl) acrylic resin and vinylidene fluoride resin, resin combination can also be with Contain the resin other than these resins.

At least one resin contained by these resin combinations contains alkali metal.In (methyl) acrylic resin or inclined two Fluoroethylene resin be as obtained from emulsion polymerization in the case of, alkali metal for example can in resin remaining emulsifier Sodium or potassium.The total content of alkali metal is fewer, and the film containing the layer formed by resin combination is long in the environment of high temperature and humidity Phase in use, more have the tendency that the transparency do not reduce, therefore preferably.

The content of alkali metal, relative to the resin of whole contained by resin combination and 100 mass parts of total amount of alkali metal, Usually 50ppm or less.The content of alkali metal is preferably 30ppm hereinafter, more preferably 10ppm is hereinafter, further preferably 1ppm is not hereinafter, include alkali metal substantially particularly preferably.In order to make the content of the alkali metal in resin within the above range, only The washing procedure that reduce the usage amount of the compound containing alkali metal in resin polymerization or increase after polymerization contains to remove There is the compound of alkali metal.The content of alkali metal can for example pass through inductivity coupled plasma mass spectrometry analytic approach (ICP/ MS it) finds out.As inductivity coupled plasma mass spectrometry analytic approach, as long as example, by the sample strip of measurement by high temperature ashing Fusion method, high temperature ashing acid-soluble method, Ca addition ashing acid-soluble method, burning absorption process, low temperature dry ashing acid-soluble method etc. are suitable Method sample ashing is dissolved in acid, which constant volume and analyzed with inductivity coupled plasma mass spectrometry Method measures alkali metal amount.

((methyl) acrylic resin)

As (methyl) acrylic resin, for example, (the first such as (methyl) acrylate and (methyl) acrylonitrile can be enumerated Base) homopolymer of acrylic monomer, (methyl) acrylic monomer of more than two kinds copolymer, acrylic monomer and third The copolymer etc. of monomer other than alkene acrylic monomer.It should be noted that in the present specification, term " (methyl) acrylic acid " is Refer to " acrylic acid " or " methacrylic acid ".

It is excellent from the aspect with excellent hardness, weatherability, the transparency etc. as (methyl) acrylic resin Choosing uses methacrylic resin.Methacrylic resin be using methacrylate (alkyl methacrylate) as The polymer of the monomer of main body, for example, can enumerate the homopolymer (polyalkyl methacrylate) of methacrylate, 2 kinds with On the copolymer of methacrylate, the methacrylate of 50 mass % or more and 50 mass % methacrylic acids below The copolymer etc. of monomer other than ester.In the case where the copolymer of monomer other than methacrylate and methacrylate, Relative to the total amount of monomer, preferred methacrylate is 70 mass % or more, and other monomers be 30 mass % hereinafter, More preferable methacrylate is 90 mass % or more, and other monomers are 10 mass % or less.

As the monomer other than methacrylate, acrylate can be enumerated, intramolecular has the carbon-to-carbon of a polymerism The monofunctional monomer of double bond.

As monofunctional monomer, for example, the styrene list such as styrene, α-methylstyrene and vinyltoluene can be enumerated Body；The cyanidings alkenyl such as acrylonitrile and methacrylonitrile；Acrylic acid；Methacrylic acid；Maleic anhydride；N- substituted maleimide amine； Deng.Also, from the viewpoint of heat resistance, phenyl maleimide, N-cyclohexylmaleimide and methyl Malaysia can also be made The N- substituted maleimide amine such as acid imide is copolymerized, can also in strand (in the main framing also referred to as in polymer or In main chain) import lactone ring structure, glutaric anhydride structure or glutarimide structure etc..

As (methyl) acrylic resin, more specifically, the resin of (a1) or (a2) preferably below.

(a1) homopolymer of methyl methacrylate.

(a2) come containing 50~99.9 mass % from the structural unit of methyl methacrylate and 0.1~50 mass % Derived from the copolymer of at least one structural unit of (methyl) acrylate indicated by following formula (1).Here, structural unit contains Amount can measure peak area corresponding to each monomer by analyzing obtained polymer with Thermal decomposition gas chromatography method It calculates.

In formula (1), R₁Indicate hydrogen atom or methyl, R₁R when for hydrogen atom₂Indicate the alkyl of carbon number 1~8, R₁For methyl When R₂Indicate the alkyl of carbon number 2~8.As by R₂The alkyl of the carbon number 2~8 of expression, can enumerate ethyl, propyl, isopropyl, fourth Base, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl etc..

When 230 measured under 3.8kg load DEG C of (methyl) acrylic resin melt mass flow rate (with Under, it is also denoted as MFR sometimes.) it is usually 0.1~20g/10 minutes, preferably 0.2~5g/10 minutes, more preferably 0.5~3g/ 10 minutes.When MFR is excessive, the film strength having the tendency that is reduced, and when MFR is too small, has the tendency that film forming reduction.MFR It can be according to JISK 7210:1999 " plastics-thermoplastic melt mass flow rate (MFR) and volume melt-flow Method specified in the test method of rate (MVR) " is measured.For poly- (methyl methacrylate) system material in temperature 230 DEG C, be measured under load 3.80kg (37.3N), be exactly specified in the JIS.

The weight average molecular weight that (methyl) acrylic resin is measured by GPC (hereinafter, be also denoted as Mw sometimes.) preferably It is 100,000~300,000, more preferably 120,000~250,000, further preferably 150,000~200,000.For Obtained film, Mw is bigger, has transparency when being exposed under hot and humid environment as 60 DEG C and relative humidity 90% higher Tendency, however when Mw is excessive, have the tendency that film forming reduction.

From the viewpoint of heat resistance, the vicat softening temperature of (methyl) acrylic resin (hereinafter, be also denoted as sometimes VST.) it is preferably 90 DEG C or more, more preferably 100 DEG C or more, further preferably 102 DEG C or more.According to JIS K 7206: 1999, VST is measured using the B50 method being described.Can type, its ratio by adjusting monomer, suitably to set Determine VST.

Above-mentioned monomer is polymerize by using method well known to suspension polymerisation, bulk polymerization etc., so as to make Make (methyl) acrylic resin.At this point, MFR, Mw, VST etc. can be adjusted to preferred by adding suitable chain-transferring agent In the range of.Chain-transferring agent is able to use suitable commercially available product.The additive amount of chain-transferring agent according to the type of monomer, its ratio, The progress such as required characteristic suitably determine.For obtained (methyl) acrylic resin, preferably alkali metal Content it is few.The usage amount for the compound that the content of alkali metal contains alkali metal when can polymerize by reducing or increase polymerize Washing procedure afterwards is adjusted to remove the compound containing alkali metal.

(vinylidene fluoride resin)

As vinylidene fluoride resin, from the viewpoint of the transparency of obtained film, can enumerate make selected from trifluoro-ethylene, Tetrafluoroethene, hexafluoropropene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene at least one monomer and vinylidene fluoride Polymer obtained by being copolymerized, polymerize vinylidene fluoride individually obtained by polymer (polyvinylidene fluoride), preferably For polyvinylidene fluoride.

Melt mass flow rate (MFR) at vinylidene fluoride resin measure under 3.8kg load 230 DEG C is usually 0.1~30g/10 minutes, preferably 0.1~25g/10 minutes.The lower limit of MFR is more preferably 0.2g/10 minutes, further preferably It is 0.5g/10 minutes.The upper limit of MFR is more preferably 20g/10 minutes, further preferably 5g/10 minutes, particularly preferably 2g/ 10 minutes.When MFR is excessive, the film having the tendency that is reduced in the transparency when used for a long time, when MFR is too small, there is film forming drop Low tendency.

The weight average molecular weight (Mw) that vinylidene fluoride resin is measured according to GPC and measured is preferably 100,000~500, 000, more preferably 150,000~450,000, further preferably 200,000~450,000, particularly preferably 350,000~ 450,000.Mw is bigger, and the transparency when film having is exposed under 60 DEG C and the hot and humid environment of relative humidity 90% is got over High tendency, however when Mw is excessive, have the tendency that film forming reduction.

Vinylidene fluoride resin industrially passes through suspension polymerization or emulsion polymerization manufacture.Suspension polymerization is to pass through Using water as medium, dispersing agent is used to disperse monomer as drop in the medium, to be dissolved in the organic peroxy in monomer Object is polymerize as polymerization initiator and is implemented, and 100~300 μm of granular polymer is obtained.Suspension polymer compared to Emulsion polymer, manufacturing process is simple, and the treatability of powder is excellent, and includes containing alkali metal unlike emulsion polymer Emulsifier, salting-out agents, therefore preferably.The content of the alkali metal of the vinylidene fluoride resin preferably obtained is few.Alkali metal The content compound that contains alkali metal when can polymerize by reducing usage amount or the washing procedure that increases after polymerization remove The compound containing alkali metal is gone to be adjusted.

Commercially available product also can be used in vinylidene fluoride resin.As the example of preferred commercially available product, can enumerate T#1300, T#1100, T#1000, T#850, the W# of " KF Polymer (registered trademark) " of KUREHACORPORATION LTD. 850, W#1000, W#1100 and W#1300, Solvay corporation " SOLEF (registered trademark) " 6012,6010 and 6008.

(other additives)

In resin combination of the invention, in a range that does not hinder the effect of the present invention, can also add usually makes Various additives.As additive, for example, stabilizer, antioxidant, ultraviolet absorbing agent, light stabilizer, hair can be enumerated Infusion, lubricant, release agent, antistatic agent, fire retardant, release agent, polymerization inhibitor, flame retardant, reinforcing agent, nucleating agent, blueing Colorants such as agent (Block Le ー イ Application Network drug) etc..

As colorant, the compound with anthraquinone skeleton, compound with phthalocyanine frame etc. can be enumerated.These chemical combination In object, the compound with anthraquinone skeleton is preferred from the viewpoint of heat resistance.

In the case that resin combination contains colorant, the content of the colorant in resin combination can according to purpose, The type etc. of colorant is properly selected.In the case where using blueing agent as colorant, content can be set to relative to 100 mass parts of resin combination are 0.01~10ppm or so.Its content is preferably 0.01ppm or more, more preferably 0.05ppm More than, further preferably 0.1ppm or more, and preferably 7ppm hereinafter, more preferably 5ppm hereinafter, further preferably 4ppm is hereinafter, particularly preferably 3ppm or less.Blueing agent can suitably use well known blueing agent, for example, can enumerate respectively Trade name Macrolex (registered trademark) Blue RR (Bayer corporation), Macrolex (registered trademark) Blue 3R (Bayer corporation), Sumiplast (registered trademark) Viloet B (Zhu Hua chemical company system) and Polysynthren (registration Trade mark) Blue RLS (CLARIANT corporation), Diaresin Violet D, Diaresin Blue G, Diaresin BlueN (more than, Mitsubishi Chemical's (strain) system).

These additives may include in the resins such as (methyl) acrylic resin or vinylidene fluoride resin, can also be with It is added in the melting mixing of aftermentioned (methyl) acrylic resin and vinylidene fluoride resin, it can also be in (methyl) propylene It adds, can also be added when making film using resin combination after the melting mixing of acid resin and vinylidene fluoride resin.

Resin combination of the invention is usually by mixing (methyl) acrylic resin and vinylidene fluoride resin It refines and obtains.The mixing for example can by containing 150~350 DEG C at a temperature of, under 10~1000/ seconds shear velocities into The method of the process of row melting mixing and implement.

Carry out melting mixing when temperature less than 150 DEG C in the case where, have a possibility that resin does not melt.On the other hand, In the case that temperature when carrying out melting mixing is greater than 350 DEG C, there is a possibility that resin thermally decomposes.In addition, being melted In the case that shear velocity when mixing was less than 10/ second, it is unable to fully a possibility that being kneaded.On the other hand, it is mixed to carry out melting In the case that shear velocity when refining is greater than 1000/ second, there is a possibility that resin is decomposed.

The resin combination that each ingredient is more uniformly mixed in order to obtain, melting mixing preferably 180~300 DEG C, more It is preferred that being carried out at a temperature of 200~300 DEG C, preferably carried out under 20~700/ seconds, more preferable 30~500/ seconds shear velocities.

As equipment used in melting mixing, common mixing machine, kneading machine can be used.Specifically, can enumerate Uniaxial kneading machine, twin shaft kneading machine, multiple screw extruder, Henschel mixer, banbury mixers, kneader, roller mill etc..And And in the case where increasing shear velocity within the above range, high shear processing unit (plant) etc. also can be used.

< film >

Film of the invention preferably comprises the layer (hereinafter, sometimes referred to as A layers) formed by the resin combination of aforementioned present invention, It can be A layers of monofilm, or the film containing A layers with 2 layers or more of other layers.The thickness of film is preferably 500~ 2000 μm, more preferably 500~1500 μm, further preferably 100~1500 μm, particularly preferably 100~1000 μm.

From the viewpoint of heat resistance, surface hardness and adaptation with aftermentioned coating, the preferably described film also contains heat Plastic resin layers.Thermoplastic resin layer can be laminated at least one face of the layer formed by resin combination of the invention, It can also be laminated by other layers, it is preferred that being contacted with the layer formed by resin combination of the invention thermoplastic is laminated Property resin layer.From the viewpoint of the shape for keeping film, thermoplastic resin layer is contained on the two sides of the A layer preferably contained by film.

The thickness of thermoplastic resin layer is preferably 10~200 μm, and more preferably 50~150 μm.Two of A layer contained by film In the case that thermoplastic resin layer is contained in face, the thickness of each thermoplastic resin layer, composition can be same or different to each other, but from guarantor From the perspective of holding the shape of film, preferably it is essentially the same as each other.

Thermoplastic resin layer is formed by thermoplastic resin.For thermoplastic resin, according to JIS K7206:1999 measurement The vicat softening temperature of thermoplastic resin is preferably 100~160 DEG C, and more preferably 102~155 DEG C, further preferably 102~ 152℃.In the case where thermoplastic resin includes a kind of resin, the vicat softening temperature of thermoplastic resin is the dimension card of the resin Softening temperature, in the case where thermoplastic resin contains multiple resins, the vicat softening temperature of thermoplastic resin is by a variety of trees The vicat softening temperature for the thermoplastic resin that rouge is formed.As the example of thermoplastic resin layer, (methyl) acrylic compounds can be enumerated Resin layer, polycarbonate resin, cyclic olefin resins layer etc..Preferably (methyl) acrylic resin or polycarbonate resin Layer.

(methyl) acrylic resin can be by a kind or more of (methyl) acrylic resin or a kind or more The compound resin shape of thermoplastic resin other than (methyl) acrylic resin of (methyl) acrylic resin and a kind or more At.For these (methyl) acrylic resins, the preferably all resins relative to formation (methyl) acrylic resin 100 mass parts contain (methyl) acrylic resins more than 50 mass parts.(first contained by (methyl) acrylic resin Base) weight average molecular weight (Mw) of acrylic resin is preferably 50,000~300,000, more preferably 70,000~250,000. (methyl) acrylic resin contained by (methyl) acrylic resin can be with the resin combination shape by aforementioned present invention At layer contained by (methyl) acrylic resin it is identical or different.Preferred thermoplastic resin layer does not include inclined difluoro second substantially Olefine resin.

As the thermoplastic resin other than above-mentioned (methyl) acrylic resin, preferably with (methyl) acrylic resin Compatible thermoplastic resin.From the viewpoint of heat resistance, the thermoplastic resin other than (methyl) acrylic resin is according to JIS The vicat softening temperature of K 7206:1999 measurement is preferably 115 DEG C or more, and more preferably 117 DEG C or more, further preferably 120 DEG C or more.

In the case that thermoplastic resin is (methyl) acrylic resin, the pencil hardness of thermoplastic resin layer is preferably HB More than, more preferably F or more, further preferably H or more.

Polycarbonate resin can be by the polycarbonate resin and 1 of a kind or more of polycarbonate resin or a kind or more Kind or more polycarbonate resin other than the compound resin of thermoplastic resin formed.These polycarbonate resins are in temperature 300 DEG C and load 1.2kg under conditions of the melt volume-flow rate that measures (hereinafter also referred to as MVR.) it is preferably 3~120cm³/ 10 minutes.MVR is more preferably 30~80cm³/ 10 minutes, further preferably 4~40cm³/ 10 minutes, particularly preferably 10~ 40cm³/ 10 minutes.MVR is less than 3cm³In the case where/10 minutes, mobility is reduced, therefore is difficult to melt to be coextruded into The tendency of the processing and formings such as type or bad order occurs sometimes.Also, MVR is greater than 120cm³At/10 minutes, there is poly- carbonic acid The tendency that the mechanical properties such as the intensity of ester resin layer reduce.MVR can according to JIS K 7210, under the load of 1.2kg, 300 It is measured under conditions of DEG C.

Polycarbonate resin is, for example, the phosphinylidyne by making various dihydroxy diaryl compounds and phosgene react Gather obtained from chlorine method or the ester-interchange method for making the carbonic esters such as dihydroxy diaryl compound and diphenyl carbonate react Object is closed, as representative polycarbonate resin, can be enumerated by bis- (4- hydroxy phenyl) propane of 2,2- (common name bisphenol-A) manufacture Polycarbonate resin.

As above-mentioned dihydroxy diaryl compound, in addition to bisphenol-A, bis- (4- hydroxy phenyl) methane, 1,1- can be enumerated Bis- (4- hydroxy phenyl) butane of bis- (4- hydroxy phenyl) ethane, 2,2-, bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4- hydroxy benzenes Base) phenylmethane, bis- (4- hydroxy phenyl -3- aminomethyl phenyl) propane of 2,2-, bis- (the 4- hydroxyl -3- tert-butyl-phenyls) third of 1,1- Bis- (4- hydroxyl -3- bromophenyl) propane of alkane, 2,2-, bis- (4- hydroxyl -3,5- dibromo phenyl) propane of 2,2-, bis- (the 4- hydroxyls-of 2,2- 3,5- dichlorophenyl) this kind of bis- (hydroxyaryl) alkanes of propane；Bis- (4- hydroxy phenyl) pentamethylene of 1,1-, bis- (the 4- hydroxyls of 1,1- Base phenyl) this kind of bis- (hydroxyaryl) cycloalkanes of hexamethylene；4,4 '-dihydroxydiphenyl ethers, 4,4 '-dihydroxy -3,3 '-two This kind of dihydroxy diaryl ethers of methyldiphenyl base ether；This kind of dihydroxy diaryl thioether class of 4,4 '-dihydroxydiphenyl thioethers； This kind of dihydroxy diaryl sulfoxide of 4,4 '-dihydroxydiphenyl sulfoxides, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfoxide Class；This kind of dihydroxy diaryl sulfone class of 4,4 '-dihydroxy-diphenyl sulfones, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfone.

These compounds are used alone or mix two or more use, in addition to these compounds, can also mix piperazine Piperazine, two pyridine hydroquinones, resorcinol, 4,4 '-dihydroxydiphenyls etc. use.

In addition it is also possible to be used in mixed way above-mentioned dihydroxy aryl compound and this kind of 3 yuan as shown below or more of phenolate Close object.As 3 yuan or more of phenol, phloroglucin, 4,6- dimethyl -2,4 can be enumerated, 6- tri--(4- hydroxy phenyl)-heptene, 2,4,6- dimethyl -2,4,6- three-(4- hydroxy phenyl)-heptane, 1,3,5- tri--(4- hydroxy phenyl)-benzene, 1,1,1- tri--(4- Hydroxy phenyl)-ethane and 2,2- it is bis--[4,4- (4,4 '-dihydroxydiphenyl)-cyclohexyl]-propane etc..

Other than polycarbonate resin is by the polycarbonate resin of a kind or more of polycarbonate resin and a kind or more In the case that the compound resin of thermoplastic resin is formed, can in the range for not damaging the transparency cooperation polycarbonate resin with Outer thermoplastic resin.As the thermoplastic resin, for example, it is preferable to (methyl) acrylic compounds tree compatible with polycarbonate resin Rouge more preferably has the methacrylic resin of aromatic rings or cycloolefin in the structure.Polycarbonate resin contains this kind of methyl When acrylic resin, the surface hardness of the polycarbonate resin enabled to is higher than to be independently formed by polycarbonate resin The case where.

As the polycarbonate resin other than above-mentioned polycarbonate resin, it can enumerate and be closed by isobide and aromatic diol At polycarbonate.For example, Mitsubishi Chemical's system " DURABIO (registered trademark) " can be enumerated.

In polycarbonate resin, within the scope of the effect of the invention, release agent, ultraviolet light can also be contained Other than the additives such as absorbent, dyestuff, pigment, polymerization inhibitor, antioxidant, fire retardant, reinforcing agent, foregoing polycarbonates resin Polymer etc..

Commercially available product also can be used in polycarbonate resin, as the example of commercially available product, can enumerate SumikaStyron 301-4,301-10,301-15,301-22,301- of Polycarbonate Limited system " Caliber (registered trademark) " 30,301-40, SD2221W, SD2201W, TR2201 etc..

Film of the invention is total light that is transparent, being measured according to JIS K7361-1:1997 in the case where visual observations Transmissivity (Tt) is preferably 88% or more, and more preferably 90% or more.Even if exposing the film to 60 DEG C and relative humidity 90% Environment lower 120 hours, the total light transmittance of film also kept the range.

Film of the invention contains (methyl) acrylic resin and vinylidene fluoride resin.It can make film of the invention is sudden and violent When being exposed in the environment of 60 DEG C and relative humidity 90% 120 hours, it is according to the mist degree (haze value) that JISK7136:2000 is measured 2.0% hereinafter, and can make yellow chromaticity (yellow colour index, Yellow Index:YI value) to be 1.5 or less.Mist degree is more preferably 1.8% hereinafter, further preferably 1.5% or less.It should be noted that for yellow chromaticity, it can be according to JIS Z 8722: 2009 calculate YI value.Vinylidene fluoride resin is more preferably 1.4 hereinafter, further preferably 1.2 or less.

Also, film of the invention stands 24 according to JIS K 6911:1995, in the environment of 23 DEG C and relative humidity 50% Hour, it is usually in the present context 3.5 or more with the dielectric constant in 3V, 100kHz that self-balancing bridge circuit method measures, it is excellent It is selected as 4.0 or more.When measurement, using commercially available equipment, such as can be with Agilent Technologies Ltd.'s " precision LCR meterHP4284A " is measured.

A contained by film of the invention layers, can by by the resin combination of aforementioned present invention for example by melting extrusion at Type method, solution curtain coating film method, pressure sintering, injection moulding etc. are formed and are manufactured.Wherein, it preferably reflects the method for forming and melts Melt extrusion moulding, the more preferable melting extrusion method of forming.

It, can be by the way that above-mentioned molding will be utilized to make this in the case where film of the invention also contains thermoplastic resin layer It for example by adhesive or is glued A layers obtained by the resin combination molding of invention, with thermoplastic resin layer obtained by addition molding Agent is connect to be bonded and manufactured, it is preferred that by by resin combination of the invention, with (methyl) acrylic resin and gather The thermoplastic resins such as carbonate resin carry out stacking integration by melting co-extrusion modling and manufacture.So altogether by melting Extrusion molding and the film manufactured usually have the tendency for being easy to carry out post forming compared to the film by fitting manufacture.

Melting co-extrusion modling is for example by resin combination and (methyl) acrylic resin and poly- carbonic acid of the invention After the thermoplastic resins such as ester resin put into 2 or 3 extruders uniaxially or biaxially respectively and respectively carry out melting mixing, by The layer formed by resin combination of the invention is laminated with thermoplastic resin layer for feed hopper die head, branch manifold die head etc. Integration and the forming process squeezed out.It is preferred that obtained film for example carries out cooling by roller unit etc., solidifies.

It is preferred that film of the invention is at least one surface, there are also for assigning selected from anti-scratch, antireflection, anti-dazzle and anti- The coating of at least one of fingerprint function.As coating, it is, for example, possible to use remember in Japanese Unexamined Patent Publication 2013-86273 bulletin The curing overlay film of load.

The thickness of coating is preferably 1 μm~100 μm, more preferably 3 μm~80 μm, further preferably 5 μm~70 μm.It is thick When spending thinner than 1 μm, it is difficult to realize function, when thickness is than 100 μ m-thick, worry the rupture of coating.

As needed, can be implemented at antireflection on the surface of coating by coating process, sputtering method, vacuum vapour deposition etc. Reason.Also, as the purpose for assigning anti-reflection effect, the antireflection in addition made can also be bonded on its single or double The sheet material of property.

The layer formed by resin combination of the invention is abbreviated as A layers, thermoplastic resin layer is abbreviated as to B layers, will be applied When layer is abbreviated as C layers, as the layer configuration example of film of the invention, following (1)~(12) can be enumerated.Wherein, consider coating and film Adaptation, scratch resistant when, there is thermoplastic resin layer on surface layer, further consider to be exposed to 60 DEG C and relative humidity 90% this When change in shape when under the hot and humid environment of sample is few, the preferred composition of (3), (4), (10) or (12), more preferable (3) or (10) composition.

(1) A layers

(2) A layers/B layers

(3) B layers/A layers/B layers

(4) B layers/A layers/B layers/A layers/B layers

(5) A layers/C layers

(6) C layers/A layers/C layers

(7) A layers/B layers/C layers

(8) C layers/A layers/B layers/C layers

(9) B layers/A layers/B layers/C layers

(10) C layers/B layers/A layers/B layers/C layers

(11) B layers/A layers/B layers/A layers/B layers/C layers

(12) C layers/B layers/A layers/B layers/A layers/B layers/C layers

< electrically conducting transparent sheet material >

Transparent conductive film is formed in at least one side of the film of aforementioned present invention, transparent conductive sheets material can be obtained.

It can be straight on the surface of film of the invention as the method for forming transparent conductive film on the surface of film of the invention The method to form transparent conductive film is connect, or may be by the way that the plastic film layer for being pre-formed with transparent conductive film is laminated on this The surface of the film of invention is come the method that forms transparent conductive film.

As the film base material for the plastic foil for being pre-formed with transparent conductive film, as long as transparent film and being capable of forming transparent The substrate of conductive film, for example, can enumerate polyethylene terephthalate, polyethylene naphthalate, polycarbonate, Acrylic resin, polyamide, the mixture of these substances or sandwich etc..Also, before forming transparent conductive film, in order to Improve surface hardness, prevent Newton's ring, assign static electricity resistance etc., it is effective for implementing coating in advance to above-mentioned film.

The method that the film layer for being pre-formed with transparent conductive film is laminated on to the surface of film of the invention, as long as without bubble Deng, equably obtain the method for clear sheet, then can be any means.It can be used using by room temperature, heating, ultraviolet light Or visible light and the method that carries out cured bonding agent and be laminated, it can also be bonded by transparent adhesive tape.

Film build method as transparent conductive film, it is known that vacuum vapour deposition, sputtering method, CVD method, ion plating method, gunite Deng can suitably use these methods according to required film thickness.

In the case where sputtering method, for example, using the common sputtering method using oxide target, the reaction using metallic target Property sputtering method etc..At this point, as reactant gas, oxygen, nitrogen etc. can be imported or and with addition ozone, plasma The means such as irradiation, ion auxiliary.Also, as needed, the biass such as direct current, exchange, high frequency can also be applied to substrate.As saturating It is compound can to enumerate indium oxide, tin oxide, zinc oxide, indium-tin for the metal oxide of transparent conductivity used in bright conductive film Oxide, tin-antimony composite oxides, zinc-aluminium composite oxide, indium-zinc composite oxide etc..Wherein, from ambient stable From the perspective of property, circuit fabrication, preferred indium-tin composite oxides (ITO).

As the method for forming transparent conductive film, coating can be applicable in containing being capable of forming the various of transparent conductivity overlay film The coating agent of electroconductive polymer, method etc. of the ionizing radiations such as irradiation heat or ultraviolet light to be solidified to form.Make For electroconductive polymer, it is known that these electroconductive polymers can be used in polythiophene, polyaniline, polypyrrole etc..

It as the thickness of transparent conductive film, is not particularly limited, in the feelings of the metal oxide using transparent conductivity Under condition, usuallyPreferablyAs long as in the range, both electric conductivity and the transparency are excellent It is different.

The thickness of electrically conducting transparent sheet material is not particularly limited, and can be selected most according to the requirement of the product description of display Suitable thickness.

< touch sensor panel >

Film and electrically conducting transparent sheet material of the invention can the transparent electrode suitably as display pannel, touch screen etc. make With.Specifically, film of the invention can be used as touch screen window material (window sheet), electrically conducting transparent sheet material is used Make the electrode base board of the touch screen of resistive film mode, capacitive way.By the way that the touch screen is configured at liquid crystal display, organic EL The front surface of display etc., the external mounted for obtaining having touch screen function (are made paper moulds) touch sensor panel outside.

< display device >

Film of the invention can be suitable for the panel display apparatus other than liquid crystal display and liquid crystal display device, for example, can It is used using the front panel as the outmost surface for being configured at display device.As the FPD dress other than liquid crystal display device It sets, organic EL display device, plasm display device, Field Emission Display (FED), SED mode plane can be enumerated and shown Device, Electronic Paper etc..For example, film of the invention can pass through bonding agent and adhesive in the case where being suitable for liquid crystal display device Equal optical cements adhesive layer is laminated on polarization plates.As bonding agent or adhesive, suitable well known substance can be used.

An example of the liquid crystal display device using film of the invention is shown with schematic cross-section in Fig. 2.Film of the invention 10 can be laminated on polarization plates 11 by optical cement adhesive layer, which can be configured at the observation side of liquid crystal cells 13.Liquid The back side of brilliant unit is commonly configured with polarization plates.Liquid crystal display device 15 is made of such component.It should be noted that figure 2 be an example of liquid crystal display device, however it is not limited to this composition.

Embodiment

Hereinafter, enumerate embodiment and the present invention is specifically described in comparative example, but the present invention is not restricted to these implements Example.

In embodiment, vicat softening temperature, the content of alkali metal, MFR, MVR, total light transmittance, mist degree and YI value make It is measured respectively with the following method.

According to JIS K 7206:1999, " plastics-thermoplastic-vicat softening temperature (VST) tries vicat softening temperature B50 method specified in proved recipe method " is measured.Using heat distortion tester, ((strain) An Tianjing mechanism makees made " 148-6 Even type ") measurement vicat softening temperature.Test film at this time is that each raw material is press-formed into 3mm thickness to be measured.

The content of alkali metal is measured by inductivity coupled plasma mass spectrometry analytic approach.

MFR is according to JIS K 7210:1999 " plastics-thermoplastic melt mass flow rate (MFR) and melt Method specified in the test method of rate of volume flow (MVR) " is measured.To the material of poly- (methyl methacrylate) system Material, is measured at 230 DEG C of temperature, loading 3.80kg (37.3N), is exactly specified in the JIS.

MVR uses (strain) Toyo Seiki according to JIS K 7210 to make made " Semi-Automatic Melt Indexer 2A " is measured under conditions of under 1.2kg load, 300 DEG C.

Total light transmittance and mist degree use foundation JIS K 7361-1:1997, and " the total light of plastics-transparent material is saturating Mist degree the transmissivity meter (" HR- of color technical research institute in (strain) village of test method-the 1 for penetrating rate: simple beam method " 100 ") it is measured.

YI value is measured using " the Spectrophotometer SQ2000 " of Japan electric color industrial (strain) system.

(Production Example 1)

Chain-transferring agent (octyl sulphur is added in 1.5 mass parts of 98.5 mass parts of mixed methyl methyl acrylate and methyl acrylate Alcohol) 0.1 mass parts of 0.16 mass parts and release agent (octadecanol), obtain monomer mixed solution.Also, in methyl methacrylate Polymerization initiator (1,1- bis- (t-butylperoxy) 3,3,5- trimethyl-cyclohexane) 0.036 mass parts are added in 100 mass parts, Obtain initiator mixed liquor.It is continuously fed into a manner of making the flow-rate ratio 8.8:1 of monomer mixed solution and initiator mixed liquor It is thoroughly mixed in type polymer reactor, polymerization to average polymerization rate is at mean residence time 20 minutes, 175 DEG C of temperature 54%, obtain partial polymer.Obtained partial polymer is heated to the devolatilization extruder of 200 DEG C and lead-in zone ventilation opening, The unreacted monomer at 240 DEG C is set to carry out water cooling from ventilation opening devolatilization, and with the condensate after molten condition extrusion devolatilization Afterwards, shearing obtains granular methacrylic resin (i).

Obtained granular methacrylic resin composition is passed through into thermal decomposition gas under conditions of as shown below Phase chromatography is analyzed, and each peak area corresponding to methyl methacrylate and acrylate is measured.As a result, methyl-prop The structural unit from methyl methacrylate of olefin(e) acid resinoid (i) is 97.5 mass %, from methyl acrylate Structural unit is 2.5 mass %.

(thermal decomposition condition)

Sample preparation: methacrylic resin composition (2~3mg of target) is accurately weighed, the gold of water guide tubulose is put into Belong to the central portion of unit, folded metal unit simultaneously presses lightly on both ends with pliers to be packaged.

Thermal decomposer: CURIE POINT PYROLYZER JHP-22 (Japanese analytical industry (strain) system)

Metal unit: Pyrofoil F590 (Japanese analytical industry (strain) system)

The set temperature of thermostat: 200 DEG C

The set temperature of insulating tube: 250 DEG C

Thermal decomposition temperature: 590 DEG C

Thermal decomposition time: 5 seconds

(gas chromatography analysis condition)

Gas chromatography analysis device: GC-14B ((strain) Shimadzu Seisakusho Ltd. system)

Detection method: FID

Column: 7G((strain) Shimadzu Seisakusho Ltd. system)

Filler: FAL-M ((strain) Shimadzu Seisakusho Ltd. system)

Carrier gas: air/N₂/H₂=50/100/50 (kPa), 80ml/ minutes

The Elevated Temperature Conditions of column: after being kept for 15 minutes at 100 DEG C, 150 DEG C is warming up to 10 DEG C/min, is protected at 150 DEG C It holds 14 minutes

INJ temperature: 200 DEG C

DET temperature: 200 DEG C

Under the conditions of above-mentioned thermal decomposition, methacrylic resin composition is thermally decomposed, measured in above-mentioned gas phase Peak face corresponding to the methyl methacrylate detected when being measured under the conditions of chromatography analysis to the decomposition product of generation Product (a₁) and acrylate corresponding to peak area (b₁).Also, peak area ratio A (=b is found out by these peak areas₁/a₁).Separately On the one hand, make weight ratio W of the acrylic ester unit relative to methyl methacrylate units₀The methacrylic of (known) The standard items of resin thermally decompose under the conditions of above-mentioned thermal decomposition, and measurement divides generation under the conditions of above-mentioned gas chromatography analysis Peak area (a corresponding to the methyl methacrylate that solution product detects when being measured₀) and acrylate corresponding to peak Area (b₀), peak area ratio A is found out by these peak areas₀(=b₀/a₀).Also, by aforementioned peak area ratio A₀With aforesaid weight ratio W₀, find out coefficient f (=W₀/A₀)。

By the way that foregoing coefficient f multiplied by aforementioned peak area ratio A, is found out contained by aforementioned methacrylic resin composition Weight ratio W of the acrylic ester unit relative to methyl methacrylate units in copolymer calculates methyl-prop by weight ratio W Ratio (quality %) and propylene of the e pioic acid methyl ester unit relative to methyl methacrylate units and the summation of acrylic ester unit Ratio (quality %) of the acid esters unit relative to aforementioned summation.

(Production Example 2)

In addition to methyl methacrylate is become 95.0 mass parts, methyl acrylate is become to 5.0 mass parts, chain-transferring agent Become other than 0.08 mass parts, got similarly granular methacrylic resin (ii) with Production Example 1, measures structure list The content of member.The structural unit from methyl methacrylate of methacrylic resin (ii) is 94.7 mass %, is come Structural unit derived from methyl acrylate is 5.3 mass %.

(Production Example 3)

In addition to methyl methacrylate being become 97.7 mass parts, methyl acrylate being become to 2.3 mass parts, by chain tra nsfer Agent becomes other than 0.05 mass parts, gets similarly granular methacrylic resin (iii) with Production Example 1, measurement knot The content of structure unit.The structural unit from methyl methacrylate of methacrylic resin (iii) is 97.0 matter % is measured, the structural unit from methyl acrylate is 3.0 mass %.

(methyl) acrylic resin and its physical property used in embodiment are shown in table 1.Methacrylic resin (i)~ It (iii) is the methacrylic resin obtained in above-mentioned Production Example, ALTUGLAS (registered trademark) HT121 is in thermoplasticity Acrylic resin used in resin layer.It should be noted that " MA " indicates the source in methacrylic resin in table In the content ratio of the structural unit of methyl acrylate.

[table 1]

The weight average molecular weight (Mw) of (methyl) acrylic resin is measured with gel permeation chromatography (GPC).Production When the standard curve of GPC, the methacrylic tree of the system of Showa electrician (strain) known to the molecular weight using narrow molecular weight distribution Rouge makes standard curve as standard reagent, by elution time and molecular weight, measures the weight average molecular weight of each resin combination.Tool For body, it is dissolved in 40mg resin in 20ml tetrahydrofuran (THF) solvent, production measurement sample.For measurement device, by 2 The column of root TOSOH CORPORATION is that " TSKgel Super HM-H " and 1 " SuperH2500 " arranged in series are arranged, For detector, using RI detector.The molecular weight distribution curve of measurement is taken the logarithm of molecular weight by horizontal axis, uses normal state Distribution function is fitted, and is fitted using the normal distyribution function of following formula.

In embodiment, the thermoplastic other than (methyl) acrylic resin used in the formation as thermoplastic resin layer Property resin, uses " レ ジ ス Off ァ イ (registered trademark) R-200 " of Denka Company Ltd..The dimension card of the resin is soft Changing temperature is 132 DEG C, and MFR is 1.8g/10 minutes.

Vinylidene fluoride resin and its physical property used in embodiment are shown in table 2.

[table 2]

The weight average molecular weight (Mw) of vinylidene fluoride is measured using GPC.When making the standard curve of GPC, polyphenyl second is used Alkene makes standard curve as standard reagent, by elution time and molecular weight, measures the weight average molecular weight of each resin.It is specific and Speech, is dissolved in 40mg resin in 20ml N-Methyl pyrrolidone (NMP) solvent, production measurement sample.For measurement device, It is set by the column of 2 TOSOHCORPORATION i.e. " TSKgel Super HM-H ", with 1 " SuperH2500 " arranged in series It sets, for detector, using RI detector.

In embodiment, for polycarbonate resin used in thermoplastic resin layer, following resin is used.Following resin It is the product of Sumika Styron Polycarbonate Ltd..

Caliber 301-15:MVR 10cm³/ 10 minutes and Mw 38,500 resins.

Caliber 301-22:MVR 22cm³/ 10 minutes and Mw 35,000 resins.

Caliber 301-30:MVR 30cm³/ 10 minutes and Mw 32,200 resins.

Caliber SD2201W:MVR 118cm³/ 10 minutes and Mw13,600 resins.

The weight average molecular weight of polycarbonate resin is measured with gel permeation chromatography (GPC).The standard for making GPC is bent When line, the methacrylic resin for using Showa electrician (strain) known to the molecular weight of narrow molecular weight distribution to make is tried as standard Agent makes standard curve by elution time and molecular weight, measures the weight average molecular weight of each resin combination.Specifically, making 40mg resin is dissolved in 20ml tetrahydrofuran (THF) solvent, production measurement sample.For measurement device, by 2 The column of TOSOHCORPORATION is that " TSKgel Super HM-H " and 1 " SuperH2500 " arranged in series are arranged, right In detector, using RI detector.

(Production Example 4)

In order to change blueing masterbatch (MB), (methyl) acrylic resin and colorant are done with the ratio of table 3 It is mixed, it usesIt is mixed that single axle extruding machine (field side plastics machinery (strain) system) carries out melting at 250~260 DEG C of set temperature It closes, obtains the masterbatch pellet through colouring.As colorant, using blueing agent (Sumika Chemitex Ltd.'s " Sumiplast (registered trademark) Violet B ").

[table 3]

(Examples 1 to 5 and comparative example 1~6)

The layer formed by resin combination of the invention is set as A layers, when thermoplastic resin layer is set as B layers, following institute Manufacture the film constituted indicated by B layers/A layers/B layers with showing.

Firstly, as A layers of forming material, it will be in (methyl) acrylic resin, vinylidene fluoride resin and Production Example 1 The masterbatch pellet of production is mixed with combination and ratio shown in table 4, obtains resin combination of the invention.Then, respectively Aforementioned resin is existedIn single axle extruding machine 1 and 3 (toshiba machine (strain) system), as B layers of forming materials 100 mass parts of methacrylic resin (i) are existedIt is melted in single axle extruding machine 2 (Hitachi's shipbuilding (strain) system) Melt.Then, by 250~270 DEG C of set temperature of feed hopper 4 (Hitachi's shipbuilding (strain) system) by above-mentioned fusant be laminated with As constituting by the expression of above-mentioned B layer/A layers/B layers, by branch manifold pattern head 5 (Hitachi's shipbuilding (strain) is made, 2 kind of 3 Layer assignment) It squeezes out, obtains membranaceous molten resin 6.Also, by the 1st chill roll 7 of the obtained membranaceous insertion relative configuration of molten resin 6 And the 2nd between chill roll 8, and after being then inserted between the 2nd roller 8 and the 3rd roller 9 while being wound in the 2nd roller 8, it is cold to be wound in the 3rd But roller 9 are formed, are cooled down, and the film 10 of 3 layers of composition with a thickness of thickness shown in table 4 of each layer is obtained.Obtained film 10 Total film thickness is 800 μm, and visual observations are colorless and transparent.

[table 4]

As table 1~4 find out A layers contained by the calculated value of amount of alkali metal (Na+K) be shown in table 5.

Precision LCR meter HP4284A (Agilent is used according to JIS K 6911:1995 for each film Technologies Ltd. system) measurement dielectric constant, it the results are shown in table 5.Dielectric constant is by test specimen (film) 23 DEG C and relative humidity 50% in the environment of stand 24 hours, under identical environment using self-balancing bridge circuit method measure, in 3V And numerical value when 100kHz.

Also, by obtained film is placed in the constant temperature constant humidity baking oven of 60 DEG C and absolute humidity 90% 120 hours come Carry out endurance test.For the film before and after endurance test, respectively by the haze value (mist degree) measured according to JISK7136:2000 and Table 5 is shown according to the total light transmittance (Tt) that JIS K7361-:19971 is measured.

[table 5]

(embodiment 6~8)

Other than the resin combination for becoming the ratio recorded in table 6 in addition to the group in example 4, making B layers, with embodiment 4 get similarly film.Also, for obtained film, the result of the dielectric constant and endurance test that measure similarly to Example 4 It is shown in table 7.

[table 6]

[table 7]

(comparative example 7 and 8)

By the metering system as the particle of the resin 4 of vinylidene fluoride resin and as (methyl) acrylic resin The particle of acid resin (iii) is mixed respectively with the ratio uniform recorded in table 8, then, is squeezed out using 20mm single shaft Machine (LABOPLASTOMILL, the production of (strain) Toyo Seiki are made) is kneaded at 250 DEG C, obtains that composition granule is blended.Pass through It is press-formed at 220 DEG C using the particle, obtains 800 μm of thickness of film.Also, for obtained film, with embodiment 1 The result of the endurance test similarly measured is also depicted in table 8.

[table 8]

(embodiment 9 and comparative example 9)

By the metering system as the particle of the resin 1 of vinylidene fluoride resin and as (methyl) acrylic resin The particle of acid resin (i) is mixed respectively with the ratio uniform recorded in table 9, then, uses 20mm single axle extruding machine (LABOPLASTOMILL, the production of (strain) Toyo Seiki are made) is kneaded at 250 DEG C, obtains that composition granule is blended.By making It is press-formed at 220 DEG C with the particle, obtains 800 μm of thickness of film.Also, it is same with embodiment 1 for obtained film The result of the dielectric constant and endurance test that measure to sample is also depicted in table 9.

[table 9]

(embodiment 10)

It will be used in film obtained in Examples 1 to 9 as front panel (display window material), so as to manufacture figure The display device of composition shown in 2 sectional view.

(embodiment 11~18)

When the layer formed by resin combination being set as A layers, thermoplastic resin layer being set as to B layers, manufacture as described below is by B The film of composition represented by layer/A layers/B layers.

Firstly, as A layers of forming material, it will be in (methyl) acrylic resin, vinylidene fluoride resin and Production Example 1 The masterbatch pellet of production is mixed with combination and ratio shown in table 10, obtains resin combination of the invention.In addition to resin Other than composition is different, processing method is carried out in method identical with Examples 1 to 5.

[table 10]

By obtained film as table 1 and 3 find out A layers contained by alkali metal (Na+K) amount calculated value and use with it is upper State the dielectric constant shown in table 11 of the identical method measurement of method.Also, obtained film is placed in 60 DEG C and absolute humidity The result of endurance test in 120 hours shown in table 11 in 90% constant temperature constant humidity baking oven.

[table 11]

(embodiment 19~22)

Other than using polycarbonate resin in B layers, film is made in method identical with Examples 1 to 5.A layers and B layers Resin with being combined into and ratio shown in table 12.

[table 12]

By obtained film, as table 1 and 3 find out A layers contained by alkali metal (Na+K) amount calculated value and use with it is upper State the dielectric constant shown in table 13 of the identical method measurement of method.Also, obtained film is placed in 60 DEG C and absolute humidity The result of endurance test in 120 hours shown in table 13 in 90% constant temperature constant humidity baking oven.

[table 13]

In addition, measuring result shown in table 14 obtained by falling sphere intensity for obtained film.Falling sphere intensity is by the iron of 25g Ball is fallen from specified height, the height of measurement film rupture.

[table 14]

Example number

Embodiment 4

Embodiment 11

Embodiment 12

Embodiment 19

Embodiment 20

Embodiment 21

Embodiment 22

Falling sphere intensity (cm)

10

10

10

≥100

≥100

≥100

15

Industrial availability

The layer formed by resin combination of the invention and the film of the invention containing this layer have high dielectric constant, and And even if in the environment of high temperature and humidity for a long time using be able to maintain the transparency, accordingly act as smart phone, portable game The front panel of the display devices such as gaming machine, audio player and plate computer terminal.

Description of symbols

1 single axle extruding machine (fusant for squeezing out (methyl) acrylic resin)

2 single axle extruding machines (fusant for squeezing out resin combination of the invention)

3 single axle extruding machines (fusant for squeezing out (methyl) acrylic resin)

4 feed hoppers

5 branch manifold pattern heads

6 membranaceous molten resins

7 the 1st chill rolls

8 the 2nd chill rolls

9 the 3rd chill rolls

10 films

11 polarization plates

12 optical adhesives

13 liquid crystal cells

15 liquid crystal display devices

Claims (17)

1. a kind of film, contains the layer formed by following resin combinations, the resin combination contains (methyl) acrylic compounds Resin, vinylidene fluoride resin and colorant, wherein

Relative to the 100 mass % of summation of (methyl) acrylic resin and vinylidene fluoride resin, contain 35 mass % respectively ~45 mass % (methyl) acrylic resins and the 65 mass % vinylidene fluoride resins of mass %~55, should (methyl) acrylic acid The weight average molecular weight Mw of resinoid is 100,000~300,000,

Melt mass flow rate MFR at the vinylidene fluoride resin measure under 3.8kg load 230 DEG C is 0.1g/ 10 minutes~30g/10 minutes, the weight average molecular weight Mw for being measured and being measured according to GPC was 100,000~500,000,

At least one resin contained by resin combination contains alkali metal, relative to all resins contained by resin combination and alkali 100 mass parts of total amount of metal, the content of alkali metal are 50ppm or less.

2. film as described in claim 1, wherein (methyl) acrylic resin is the resin of (a1) or (a2) below,

(a1) homopolymer of methyl methacrylate,

(a2) structural unit containing 50 mass of mass %~99.9 % from methyl methacrylate and 0.1 mass %~50 Quality % derives from the copolymer of at least one structural unit of (methyl) acrylate indicated by following formula (1),

In formula, R₁Indicate hydrogen atom or methyl, R₁R when for hydrogen atom₂Indicate the alkyl of carbon number 1~8, R₁R when for methyl₂Indicate carbon The alkyl of number 2~8.

3. film as claimed in claim 1 or 2, wherein the weight average molecular weight Mw of (methyl) acrylic resin be 120,000~ 250,000。

4. film as claimed in claim 1 or 2, wherein vinylidene fluoride resin is polyvinylidene fluoride.

5. film as described in claim 1, wherein the film with a thickness of 100 μm~2000 μm.

6. film as claimed in claim 1 or 2, wherein the film also contains thermoplastic resin layer.

7. film as claimed in claim 1 or 2, wherein contain thermoplastic resin on the two sides of the layer formed by resin combination Layer.

8. film as claimed in claim 6, wherein thermoplastic resin layer is (methyl) acrylic resin or polycarbonate resin Rouge layer.

9. film as claimed in claim 6, wherein thermoplastic resin layer is by relative to the whole for forming the thermoplastic resin layer The layer that the resin that 100 mass parts of resin contain 50 mass parts or more (methyl) acrylic resin is formed.

10. film as claimed in claim 8 or 9, wherein the weight of (methyl) acrylic resin contained by thermoplastic resin layer is equal Molecular weight is 50,000~300,000.

11. film as claimed in claim 6, wherein thermoplastic resin layer with a thickness of 10 μm~200 μm.

12. film as claimed in claim 6, wherein the vicat softening temperature of thermoplastic resin layer is 100 DEG C~160 DEG C.

13. film as described in claim 1, wherein the film to be exposed in the environment of 60 DEG C and relative humidity 90% 120 hours When, the mist degree of the film is 2% hereinafter, and dielectric constant is 4.0 or more.

14. the film as described in claims 1 or 2 or 13, wherein at least one surface, there are also be selected from anti-scratch for assigning The coating of at least one of wound, antireflection, anti-dazzle and anti-fingerprint function.

15. a kind of display device contains film described in any one of claim 1~14.

16. a kind of polarization plates with film are obtained by film and polarization plates described in any one of stacking claim 1~14.

17. a kind of display device contains the polarization plates with film described in claim 16.